Spectrometer sequential readout system

ABSTRACT

A spectrometer readout system with storage capacitors for temporarily storing output signals generated by a series of photomultiplier tubes that are positioned to monitor selected spectral lines. A voltage-time converter sequentially discharges the capacitors to a preset level and converts the stored voltages into signals that are related logarithmically to a known signal and an unknown signal. The output of the voltage-time converter defines the log discharge time period which is measured and stored by a computer.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to spectrometer readout systems and, more particularly, is directed toward high-speed sequential readout spectrometer systems.

2. Description of the Prior Art 2. A direct reading spectrometer is an apparatus adapted to indicate automatically the chemical composition of a specimen for determining the intensity distribution of radiation of characteristic wavelengths emitted by the specimen under excitation. Typically, a direct reading spectrometer comprises an entrance slit that transmits radiation from an electrically excited specimen against a diffraction grating that disperses the radiation into a spectrum. A spectrometer also includes a plurality of exit slits arrayed at selected spaced intervals for transmitting the radiation of preselected wavelengths to photocell channels in order to determine the differing intensities of the radiation at these wavelengths.

In an automatic spectrometer, described in U.S. Pat. No. 3,531,202, the output of a series of photomultiplier tubes positioned to monitor selected spectral lines is temporarily stored on capacitors. An analog to digital converter converts the stored voltages into digital form which is logarithmically related to a known signal and an unknown signal. The output of the converter, the log discharge time period, is measured and stored by a time register scaler. A computer and programmer are operatively connected to the converter and the register with the computer being adapted to provide an output which is a representation of the direct percentage of concentration of the monitored element. The programmer controls the sequence operation of the system and also provides an output to a disc or printer.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide improvements in high-speed sequential readout spectrometer systems.

Another object of this invention is to provide a solid state high speed automatic sequential readout spectrometer system with simplified circuitry and increased flexibility.

The invention features a spectrometer readout system for temporarily storing the output signal of a series of photomultiplier tubes positioned to monitor selected spectral lines, and a voltage-time converter for discharging the stored signals and converting the stored voltages into a form which is logarithmically related to a known signal and an unknown signal. The output of the converter is the log discharge time period which is measured and stored by a computer. A computer or programmer controls sequential operations of the system and computations for determining concentration of the monitored element, and generates data signals to a tape, printer or the like.

Other objects of the present invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the apparatuses and systems, together with their parts, elements and interrelationships that are exemplified in the following disclosure, the scope of which will be indicated in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

A fuller understanding of the nature and objects of the present invention will become apparent upon consideration of the following detailed description taken in connection with the accompanying drawings, wherein:

FIG. 1 is a block diagram, in somewhat schematic form, of a spectrometer readout system embodying the present invention;

FIG. 2 is a simplified schematic diagram illustrating the transfer-discharge circuitry;

FIG. 3A and 3B are waveforms illustrating certain principles of the invention; and

FIG. 4 is a schematic diagram of the sequential measurement system and voltage-to-time converter.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Referring now to the drawings, particularly to FIG. 1, reference character 10 generally indicates an electrically excited gap in which a specimen is placed for excitation. The resulting radiation is passed through an entrance slit 12 against a curved diffraction grating 14 which disperses the radiation into a spectrum, rays of which are shown at 16. These spectral components pass through a plurality of exit slits 18 distributed in predetermined spaced relation in an arc oppositely the grating for transmitting isolated wavelength of the spectrum. A bank of photocells 20 is provided to receive wavelengths 16 of which one will be considered as a reference spectrum line 22. In the illustrated embodiment, one of the photocells 20 that is positioned to receive reference spectrum line 22 is denoted by reference character 24. The photocells 20 are positioned to receive the spectrum lines 16 and each of the photocells generates a signal for a wavelength intensity comparison. The spark gap 10 is actuated by a drive unit 26 which receives appropriate timing signals by a lead 28 from a control unit 30. In practice, a shutter 34 is disposed between the spark gap 10 and the slit 12. The control unit 30 provides flush, burn and preburn control operations of the spark gap 10.

A shutter drive 36, also actuated by the control unit 30, is operatively connected to the shutter 34 and is adapted to open and close the shutter for preselected periods. The photocells 20, for example photomultiplier tubes, are energized from a suitable power source 38 provided with the usual sensitivity controls 40. The output of each photomultiplier tube is connected by leads 42 to capacitor integration circuits and multiplexers generally indicated by reference character 44 in FIG. 1.

In operation, the capacitors within the unit integrate the outputs of the photomultiplier tubes 20 during the expose period. During the measurement cycle, the capacitor voltages are fed sequentially to a voltage-to-time converter 46 in which log measurements are performed. The output from the converter 46 is the log discharge time period t_(x) which is measured and stored by a digital computer 48 via an interface 50. The principles of operation for the system are presented in FIG. 2.

Referring now to FIG. 2, it will be seen that the output from reference photomultiplier tube 24 is applied to a reference section 50 and the outputs from element photomultiplier tubes 20 are applied selectively to element sections 52, one of which is shown. Reference section 50 includes an integration capacitor 54 and switching devices 56, 58, and 60, for example, solid state MOSFET switches. Element section 52 includes a integration capacitor 62 and switching devices 64, 66 and 68, for example solid state MOSFET switches. In the illustrated embodiment, the sections for determining element concentration, reference or background are identical.

The output of each section is connected to a common junction 70 at the input of a voltage follower 72. A switch 74, for example a solid state MOSFET switch, is connected between the output of voltage follower 72 and the input of level sensor or discriminator 76, the output of which is connected to a digital computer 78 or a counter. An RC network 80, which includes a measuring capacitor 82 and a resistor 84, is connected between switch 74 and discriminator 76. A switch 86, for example a solid state MOSFET switch, is connected between the input of discriminator 76 and one side of resistor 84, the other side of the resistor being connected to a return 88.

During the exposure period, each integration capacitor is charged to a particular voltage level defined by the output of its associated photomultiplier tube 20. That is, during the exposure period switches 56, 60 in the reference channel 50 and switches 64, 68 in the element channels 52 are opened and switches 58, 66 are closed. As indicated in FIG. 2, the reference voltage on integration capacitor 54 is denoted V_(r) and the element voltages on integration capacitor 62 is denoted V_(x), V_(r) always being greater than V_(x). In the manner hereinafter described, the voltage on each integration capacitor is sequentially converted to a time period t, which is measured and stored by digital computer 78. In the illustrated embodiment, the sequence of operation is controlled by computer 78.

After the exposure period, switches 58 and 66 are opened. Although not shown, it is to be understood that the other element capacitors are isolated also from their associated photomultiplier tubes by similar switching devices in their respective channels. During this isolation period, switch 86 is closed and measuring capacitor 82 is discharged. Next, switches 60 and 74 are closed and switch 86 is opened. In consequence, the voltage V_(r) on reference capacitor 54 is transfered to measuring capacitor 82. Next, switches 60 and 74 are opened and switch 86 is closed. Measuring capacitor 82 is discharged through switch 86 and resistor 84 to a preset level L (FIG. 3A) as established in discriminator 76. The discharge time t_(r) of the reference voltage V_(r) on measuring capacitor 82, which is determined by the time constant of RC network 80, is stored in computer 78 for further computation.

A similar operation is sequentially performed on each of the element capacitors. That is, switches 68 and 74 are closed and switch 86 is opened. The element voltage V_(x) on element capacitor 62 is transfered to measuring capacitor 82. Next, switches 68 and 74 are opened and switch 86 is closed. Measuring capacitor 82 is discharged through switch 86 and resistor 84 to the preset level L (FIG. 3B) which is preset in discriminator 76. That is, discharge time constant of measuring capacitor 82 is the same for the reference voltage and for the element voltages, in each instance the measuring capacitor being discharged to the same level. The discharge time t_(e) of element voltage V_(x) on measuring capacitor 82 is stored in computer 78 for further computation. In a similar manner, the voltages stored on the remaining element capacitors are sequentially transferred to measuring capacitor 82 which is discharged at the completion of the transfer step of each element voltage.

The measurement technique described in U.S. Pat. No. 3,531,202 utilizes a logarithmic voltage to time conversion method to obtain a value which is the logarithm of the ratio of an unknown voltage to a reference voltage. In the present invention, voltage to time conversion is accomplished by sequentially transferring the voltage on each integration capacitor to a measuring capacitor that is discharged at the end of each transfer period to a common low voltage level L, (for example 25mV). The difference in discharge time t_(x), using a common RC time constant, between the voltage V_(r) from the reference capacitor and the voltage V_(x) from an element capacitor (t_(r) - t_(e)) represents the log of the ratio.

The equations are: ##EQU1##

The log of equation (4) is ##EQU2## which converts to

    t.sub.x = t.sub.r - t.sub.e = - RC.sub.m 1n (V.sub.x /V.sub.r ) (6)

A basic implementation of the sequential measurement system and the voltage-to-time converter is shown in FIG. 4. As previously discussed in connection with FIG. 2, a plurality of like sections are associated with a series of photomultiplier tubes, one section receiving the output from one photomultiplier. In the schematic diagram of FIG. 4, two sections are shown, corresponding components of the like sections being distinguished by a prime notation. In alternative embodiments, it is to be understood that the number of sections is other than two, for example four, six or some other number. The circuitry now to be described utilizes high quality amplifiers, low leakage capacitors and high performance switches for optimum system performance and accuracy.

In the sequence of operations of the circuitry in FIG. 4, during the burn or exposure period, switches 90 and 90' connecting integrating capacitors 92 and 92' integrate the photomultiplier tube output currents. The capacitance of integrating capacitors 92 and 92' can be varied by optional capacitor-switch networks 93 and 93', respectively. During the exposure period, switches in multiplexers 100 and 100' are opened. Upon completion of the exposure period, switches 90 and 90' are opened and integration capacitors 92 and 92' are disconnected from the photomultiplier tubes. Completion of the exposure period signals initiation of the measurement period.

During the measurement period, the charges on capacitors 92, 92' are transferred sequentially to a measuring capacitor 102. Firstly, measuring capacitor 102 is charged to the same voltage as exists on capacitor 92 by closing of switches 104, 106 and 108, switch 104 being a part of multiplexer 100. The charge on capacitor 92' is transferred through closed switch 104', a voltage follower 110', switch 106', a common junction 112 and switch 108 to measuring capacitor 102. Since the input inpedance of voltage follower is extremely high, in the order of 10¹² ohms, this operation is performed while leaving the voltage on capacitor 92 essentially unchanged. Having charged measuring capacitor 102, switch 108 is then opened and the measuring capacitor is discharged logarithmically to a predetermined level via a resistor 112, an amplifier 114 and a trigger 116. Resistor 112 is the log discharge resistor for measuring capacitor 102 since it is connected to an input of amplifier 114 which is maintained at ground potential. Resistor 112 serves as the input resistor to amplifier 114 whose output is a positive voltage which is proportional to the ratio of feedback resistor 118 to resistor 112. As soon as the voltage on measuring capacitor 102 has discharged to the preset level, trigger 116 generates a stop signal that is applied to a computer or counter (not shown) for terminating the counting period during which measuring capacitor is discharged. The voltages on the remaining integration capacitors are transferred sequentially to measuring capacitor 102, which is discharged at the end of each transfer period in the manner described.

As shown in FIG. 4 each section includes switches 120, 122, 124 and 126. When switches 120 and 124 are closed, a test voltage charges capacitor 92 to a known voltage. Integration capacitor 92 is discharged through closed switches 120 and 122. Switch 126 is provided for grounding the input voltage follower 110.

The invention thus features a spectrometer readout system having a plurality of storage means for temporarily storing the output of a series of photomultiplier tubes positioned to monitor selected spectral lines and the voltage-to-time converter for converting the voltages stored in the storage means into a form which is logarithmically related to a known and an unknown signal by sequentially transferring the stored voltages to a measuring capacitor and discharging the measuring capacitor to a preset level after each transfer. The output of the voltage-to-time converter is the log discharge time period which is measured and stored by a computer. A computer or programmer controls the sequence operations of the stystem, conputation for determining the concentration of the monitored element, required corrections and provides an output to a disc 128, a printer 130 or the like.

Since certain changes may be made in the foregoing disclosure without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description and depicted in the accompanying drawings be construed in an illustrative and not in a limiting sense. 

What is claimed is:
 1. In a direct reading spectrometer for dispersing light from an excited specimen into its characteristic spectrum, an apparatus for generating data signals logarithmically related to the concentration of elements in said specimen, said apparatus comprising:(a) a plurality of photocells mounted on said spectrometer for receiving different portions of said spectrum, each of said photocells converting light energy from a selected portion of the spectrum into electrical energy; (b) a plurality of storage means operatively connected to said photocells for storing an unknown electrical charge corresponding to the intensity of the monitored spectrum portion, each one of said storage means being connected to only one of each of said photocells, one of said storage means operatively connected to one of said photocells at a reference position for storing a charge corresponding to the intensity of a reference portion of said spectrum; (c) a measuring capacitor; (d) first means for controlling the sequence of operation of the parts of the apparatus; (e) first switching means controlled by said first means and connected between said storage means and said measuring capacitor for sequentially transferring said stored charge on said storage means to said measuring capacitor; and (f) second means for discharging said measuring capacitor to a predetermined level; (g) said measuring capacitor is discharged to said predetermined level after each said transfer of said stored charge on each said storage means to said measuring capacitor by said first switching means, the time period during which said measuring capacitor is discharged for each said storage means is the log discharge time period for the element associated with that storage means.
 2. The apparatus as claimed in claim 1 wherein said storage means are capacitors.
 3. The apparatus as claimed in claim 1 wherein said second means includes a discriminator and resistor means, said resistor means connected between an input of said discriminator and a return, second switching means controlled by said first means and connected to said resistor means for discharging said measuring capacitor, said resistor means and said measuring capacitor constituting the discharge time constant for said measuring capacitor.
 4. The apparatus as claimed in claim 3 including third switching means controlled by said first means and connected between said photocells and said storage means for isolating said storage means from its associated photocell.
 5. The apparatus as claimed in claim 4 including a voltage follower and fourth switching means, said first switching means connected between each of said storage means and an input of said voltage follower, said fourth switching means controlled by said first means and connected between an output of said voltage follower and said measuring capacitor.
 6. The apparatus as claimed in claim 1 wherein said first means includes a computer which stores said log discharge time period.
 7. In a direct reading spectrometer for dispersing light from an excited specimen into its characteristic spectrum, an apparatus for generating data signals logarithmically related to the concentration of elements in said specimen, said apparatus comprising:(a) a plurality of photomultiplier tubes mounted on said spectrometer for receiving different portions of said spectrum, each said photomultiplier tube converting light energy from a selected portion of the spectrum into electrical energy; (b) a plurality of storage capacitors operatively connected to said photomultiplier tubes for storing an unknown electrical charge corresponding to the intensity of the monitored spectrum portion, each one of said storage capacitors being connected to only one of each of said photomultiplier tubes, one of said storage capacitors operatively connected to one of said photomultiplier tubes at a reference position for storing a charge corresponding to the intensity of a reference portion of said spectrum; (c) a measuring capacitor; (d) a computer for controlling the sequence of operation of the parts of the apparatus; (e) first switching means controlled by said computer for connecting and disconnecting said storage capacitors and said photomultiplier tubes; (f) second switching means controlled by said computer for connecting and disconnecting said storage capacitors and said measuring capacitor; and (g) means for discharging said measuring capacitor to a predetermined level; (h) said second switching means sequentially connecting said storage capacitors to said measuring capacitor for sequentially transferring said charge stored on said storage capacitors to said measuring capacitor, said measuring capacitor is discharged to said predetermined level after each said transfer, the time period during which said measuring capacitor is discharged is stored in said computer, said time period during which said measuring capacitor is discharged constitutes the log discharge time period for the element associated with said storage capacitor from which the stored charge is transferred to said measuring capacitor.
 8. The apparatus as claimed in claim 7 wherein said means for discharging includes resistor means and discriminator means, said measuring capacitor discharge through said resistor means until said measuring capacitor is discharged to said predetermined level established by said discriminator means.
 9. The apparatus as claimed in claim 8 including third switching means controlled by said computer for connecting and disconnecting said measuring capacitor and said resistor means, said measuring capacitor is discharged when said resistor means and said measuring capacitor are connected.
 10. The apparatus as claimed in claim 9 including a voltage follower connected between said storage capacitors and said measuring capacitor. 